(7S,8S,R-biar)-6,7,8,9-tetrahydro-1,3,12,13,14-pentamethoxy-7,8-dimethyl-2,7-dibenzocyclooctenediol

• 分子结构分类: 有机化合物 - 苯丙烷和聚酮 - 单宁
• 英文名称: (7S,8S,R-biar)-6,7,8,9-tetrahydro-1,3,12,13,14-pentamethoxy-7,8-dimethyl-2,7-dibenzocyclooctenediol
• 英文别名: 2-norschizandrin；(9S,10S)-3,5,14,15,16-pentamethoxy-9,10-dimethyltricyclo[10.4.0.02,7]hexadeca-1(16),2,4,6,12,14-hexaene-4,9-diol
• 化学式: C₂₃H₃₀O₇
• 分子量: 418.487
• InChiKey: NJULGPXGNGYLKI-MYODQAERSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  3.7
• 重原子数：
  30
• 可旋转键数：
  5
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.48
• 拓扑面积：
  86.6
• 氢给体数：
  2
• 氢受体数：
  7

反应信息

• 作为反应物：
  描述：

  乙酸酐 、 (7S,8S,R-biar)-6,7,8,9-tetrahydro-1,3,12,13,14-pentamethoxy-7,8-dimethyl-2,7-dibenzocyclooctenediol 在 吡啶 作用下， 以4.0 mg的产率得到Acetic acid (6S,7S)-6-hydroxy-1,3,10,11,12-pentamethoxy-6,7-dimethyl-5,6,7,8-tetrahydro-dibenzo[a,c]cycloocten-2-yl ester
  参考文献：
  名称：

  Structure Determination of Biliary Metabolites of Schizandrin in Rat and Dog.

  摘要：

  After oral administration of schizandrin (1) to rat, the bile was collected and treated with β-glucuronidase and arylsulfatase. Eleven metabolites, SZ-M0 (3), SZ-M1 (4), SZ-M2 (5), SZ-M3 (6), SZ-M4 (7), SZ-M5 (8), SZ-M6 (9), SZ-M7 (10), SZ-M8 (11), SZ-M9 (12) and SZ-M10 (13) were isolated from the bile treated with the enzymes. The bile after oral administration of 1 to dog was collected and treated with enzymes in the same way, and eight metabolites, 3-8, 10 and SZ-MD2 (14) were isolated from the bile treated with enzymes. The structures of these metabolites were determined on the basis of chemical and spectral studies. The major metabolite in the bile of rat was 7 and the major metabolites in the bile of dog were 7 and 14.

  DOI：

  10.1248/cpb.43.121
• 作为产物：
  描述：

  (E)-3-(methoxycarbonyl)-4-(3,4,5-trimethoxy-phenyl)but-3-enoic acid 在 palladium on activated charcoal 吡啶 、 氢氧化钾 、 sodium tetrahydroborate 、 lithium aluminium tetrahydride 、 bis(acetylacetonato)manganese(II) 、 hexaaquairon(III) perchlorate 、 bis(1,5-cyclooctadiene)rhodium(I) tetrafluoroborate 、 苯硅烷 、 氢气 、 氧气 、 potassium carbonate 、 (4R-trans)-<(2,2-dimethyl-1,3-dioxolane-4,5-diyl)bis(methylene)>bis 、 三乙胺 、 三氟乙酸 、 calcium chloride 作用下， 以 四氢呋喃 、 甲醇 、 乙醇 、 二氯甲烷 、 乙酸乙酯 、 异丙醇 、 丙酮 为溶剂， 反应 92.25h， 生成 (7S,8S,R-biar)-6,7,8,9-tetrahydro-1,3,12,13,14-pentamethoxy-7,8-dimethyl-2,7-dibenzocyclooctenediol
  参考文献：
  名称：

  五味子素代谢物的总合成

  摘要：

  实现了五味子素代谢物的总合成。通过相应的3-苄基-1-亚苄基丁内酯的氧化偶合反应，以光学纯净的形式制备了四环内酯中间体（13a-e）。Mukaiyama水合13b提供了羟基内酯（14），将其转化为SZ-M3（4）。通过连续的双键迁移到15a-e，将内酯环还原成烯丙基二醇（32a-e）和连续的双键迁移，引入了代谢物（4-11）常见的C6,7-二醇部分。乙二醇的形成。然后，甲磺酸酯33的还原完成了代谢物的合成。

  DOI：

  10.1016/0040-4020(95)00702-a

文献信息

• Transformation of Schizandrin into Gomisin A by Use of Microbial<i>O</i>-Demethylation and Chemical Reactions
  作者：Hirotoshi Kanatani、Chiaki Sakakibara、Masahide Tanaka、Kazuaki Niitsu、Yukinobu Ikeya、Takeshi Wakamatsu、Masao Maruno

  DOI：10.1271/bbb.58.1054

  日期：1994.1

  The transformation of schizandrin (I) into gomisin A (II) was accomplished by use of a combination of biotransformation and chemical reactions. The biotransformation, microbial O-demethylation of I by Cuntiinghamella echinulata var. elegans (ATCC 9245) produced two novel metabolites [3-norschizandrin (IV) and 2-norschizandrin (VI)] and two known metabolites [gomisin T (III) and 13-norschizandrin (V)]. Among those metabolites, compound III was derived to II by the O-demethylation with a Lewis acid in the presence of an acid scavenger, followed by methylenation.

  通过生物转化和化学反应相结合的方法，将五味子异黄酮（I）转化为戈米辛 A（II）。Cuntiinghamella echinulata var. elegans (ATCC 9245) 对 I 进行生物转化和微生物 O-去甲基化后，产生了两种新型代谢物[3-去甲五味子素（IV）和 2-去甲五味子素（VI）]和两种已知代谢物[五味子素 T（III）和 13-去甲五味子素（V）]。在这些代谢物中，化合物 III 是在有酸清除剂存在的情况下通过路易斯酸的 O-去甲基化反应生成 II 的，然后再进行甲基化反应。
• Regio- and stereoselective 12-O-demethylation of schizandrin into gomisin T, an important intermediate to gomisin A, by Mortierella sp. (TM-I1104)
  作者：Hirotoshi Kanatani、Susumu Terabayashi、Shuichi Takeda、Wei Li、Kazuo Koike、Tamotsu Nikaido

  DOI：10.1016/j.tetlet.2005.10.014

  日期：2005.12

  A strain TM-11104 identified as Mortierella sp. was discovered from soil as the most efficient fungus, which converted schizandrin into gomisin T in 91% regioselectivity by microbial 12-O-demethylation. Under optimum conditions, the yield of gomisin T reached around 80%. The faculty of 12-O-demethylation was specific on (+)-schizandrin (natural form) and the optical purity of gomisin T converted from (+)-schizandrin was 96% ee. (c) 2005 Elsevier Ltd. All rights reserved.
• Total syntheses of the metabolites of schizandrin
  作者：Masahide Tanaka、Yukinobu Ikeya、Hiroshi Mitsuhashi、Masao Maruno、Takeshi Wakamatsu

  DOI：10.1016/0040-4020(95)00702-a

  日期：1995.10

  The total syntheses of the metabolites of schizandrin were achieved. The tetracyclic lactone intermediates (13a–e) were prepared in optically pure form by the oxidative coupling reaction of the corresponding 3-benzyl-1-benzylidenebutyrolactones. Mukaiyama hydration of 13b afforded hydroxylactone (14), which was converted into SZ-M3 (4). The introduction of C6,7-diol moiety, which is common to the metabolites

  实现了五味子素代谢物的总合成。通过相应的3-苄基-1-亚苄基丁内酯的氧化偶合反应，以光学纯净的形式制备了四环内酯中间体（13a-e）。Mukaiyama水合13b提供了羟基内酯（14），将其转化为SZ-M3（4）。通过连续的双键迁移到15a-e，将内酯环还原成烯丙基二醇（32a-e）和连续的双键迁移，引入了代谢物（4-11）常见的C6,7-二醇部分。乙二醇的形成。然后，甲磺酸酯33的还原完成了代谢物的合成。
• Structure Determination of Biliary Metabolites of Schizandrin in Rat and Dog.
  作者：Yukinobu IKEYA、Ko SUGAMA、Masahide TANAKA、Takeshi WAKAMATSU、Hiromasa ONO、Shuichi TAKEDA、Tsutomu OYAMA、Masao MARUNO

  DOI：10.1248/cpb.43.121

  日期：——

  After oral administration of schizandrin (1) to rat, the bile was collected and treated with β-glucuronidase and arylsulfatase. Eleven metabolites, SZ-M0 (3), SZ-M1 (4), SZ-M2 (5), SZ-M3 (6), SZ-M4 (7), SZ-M5 (8), SZ-M6 (9), SZ-M7 (10), SZ-M8 (11), SZ-M9 (12) and SZ-M10 (13) were isolated from the bile treated with the enzymes. The bile after oral administration of 1 to dog was collected and treated with enzymes in the same way, and eight metabolites, 3-8, 10 and SZ-MD2 (14) were isolated from the bile treated with enzymes. The structures of these metabolites were determined on the basis of chemical and spectral studies. The major metabolite in the bile of rat was 7 and the major metabolites in the bile of dog were 7 and 14.